TW202037695A - Polarization film with adhesive layer - Google Patents

Abstract

To provide a polarization film with an adhesive layer having high durability and reworkability. A polarization film with an adhesive layer includes a polarization film and an adhesive layer. The adhesive layer includes a base polymer and a silicone oligomer. The base polymer is a (meth)acrylic polymer. The silicone oligomer is included by 0.1-20 pts.wt. based on 100 pts.wt. of the (meth)acrylic polymer. In the silicone oligomer, a Tg is -50 DEG C to 100 DEG C, a silicone functional group equivalent in a side chain is 1000 to 20000 g/mol, and a weight average molecular weight is 10000 to 300000.

Description

Polarizing film with adhesive layer

The invention relates to a polarizing film with an adhesive layer.

For liquid crystal display devices, it is indispensable to arrange polarizing films on both sides of the glass substrate forming the surface of the liquid crystal panel according to the image forming method. The polarizing film generally uses a polyvinyl alcohol-based adhesive or the like that has a protective film attached to one or both sides of a polarizing element containing a polyvinyl alcohol-based film and a dichroic material such as iodine.

When bonding the said polarizing film to a liquid crystal cell etc., an adhesive agent is usually used. In addition, since the adhesive has the advantages of instantaneous fixation of the polarizing film and no drying step for fixing the polarizing film, it is pre-installed on one side of the polarizing film as an adhesive layer. That is, a polarizing film with an adhesive layer is generally used for bonding of a polarizing film (Patent Documents 1 and 2).

In addition, when a polarizing film or a polarizing film with an adhesive layer is attached to the glass substrate of a liquid crystal panel, durability is required. For example, it is required in durability tests such as heating and humidification, which are commonly performed as environmental promotion tests. , There will be no peeling or bumping caused by the adhesive layer.

In this way, the adhesive used for the polarizing film is required to have high durability. On the other hand, in order to improve the defect or the bonding error caused by the poor process of bonding the polarizing plate, the expectation of reworkability is also increased. In recent years, according to the trend of thinning or large-scale panels, the expectation of panel regeneration has increased, so reworkability is an important item. However, there is a trade-off between high durability and reworkability, which is very difficult to balance. [Prior technical literature] [Patent literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-219765 [Patent Document 2] Japanese Patent Laid-Open No. 2018-169612

[The problem to be solved by the invention]

In view of the above-mentioned background art, there is a strong desire for a polarizing film with an adhesive layer that can have both high durability and reworkability in a trade-off relationship. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research and found that the above-mentioned problems can be solved by the polarizing film with an adhesive layer of the present invention, thereby completing the present invention.

That is, the present invention includes the following embodiments.

(1) A polarizing film with an adhesive layer, which is provided with a polarizing film and an adhesive layer, and the adhesive layer includes a base polymer and a silicone oligomer Ps, and the base polymer is (methyl) Acrylic polymer, the aforementioned polysiloxane oligomer Ps contains 0.1-20 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic polymer, and the Tg of the aforementioned polysiloxane oligomer Ps is above -50°C 100 Below ℃, the polysiloxy functional group equivalent of the side chain is 1,000 to 20,000 g/mol, and the weight average molecular weight Mw is 10,000 to 300,000.

(2) The polarizing film with an adhesive layer as described in (1) above, wherein the polysiloxane oligomer Ps includes monomer S1 having a polyorganosiloxane skeleton and the glass transition temperature of the homopolymer is Monomers above -70°C and below 180°C are used as monomer units.

(3) The polarizing film with an adhesive layer as described in (1) or (2) above, which contains an alkyl (meth)acrylate whose homopolymer has a glass transition temperature of -60°C or more and 0°C or less ( A) 80% by weight or more is used as the monomer unit of the above-mentioned base polymer.

(4) The polarizing film with an adhesive layer as described in (3) above, which further contains at least one polar monomer selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) Body (B) 0-20% by weight is used as the monomer unit of the above-mentioned base polymer.

(5) The polarizing film with an adhesive layer as described in any one of (1) to (4) above, wherein the weight average molecular weight Mw of the base polymer is 500,000 to 2.5 million.

(6) The polarizing film with an adhesive layer as described in any one of (1) to (5) above, wherein the melting temperature of the polysiloxane oligomer Ps is 0-100°C. [Effects of the invention]

According to the present invention, it is possible to provide a polarizing film with an adhesive layer capable of imparting reworkability immediately after bonding, and an adhesive force that increases after heating and imparting durability.

Hereinafter, a preferred embodiment of the present invention will be described. The industry can understand the conditions other than the items specifically mentioned in this specification and required for the implementation of the present invention based on the teachings related to the implementation of the invention described in this specification and common technical knowledge at the time of application. The present invention can be implemented based on the content disclosed in this specification and common technical knowledge in the field.

<Polarizing film with adhesive layer> The polarizing film with adhesive layer of the present invention includes a polarizing film and an adhesive layer. In the present invention, the adhesive layer may exist on one side of the polarizing film or on both sides.

The structure of the polarizing film with the adhesive layer of one embodiment is schematically shown in FIG. 1. The polarizing film 10 with the adhesive layer is configured as a polarizing film with the polarizing film 3 and the adhesive layer 4 provided on one side of the polarizing film. In FIG. 1, the polarizing film 3 includes a polarizing element 1 and protective films 2, 2 ′ provided on both sides of the polarizing element 1, but the protective film can also be provided on only one side of the polarizing element. The adhesive layer 4 is fixedly arranged on one side of the polarizing film 3, that is, the adhesive layer 4 is not intended to be separately arranged from the polarizing film 3. The polarizing film 10 with the adhesive layer is used by attaching the adhesive layer 4 to the adherend. As the separator 5, for example, a structure in which a release layer obtained with a release treatment agent is provided on one side of a sheet-like substrate (liner substrate) is preferably used to make the single side a release surface. The structure of the polarizing film with the adhesive layer is not limited to the embodiment schematically shown in FIG. 1.

<Polarizing element> The polarizing element is not particularly limited, and various polarizing elements can be used. As the polarizing element, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymer-based partially saponified film, etc., adsorbs iodine or a dichroic dye. Dichroic substances are obtained by uniaxial extension; polyene-based alignment films such as dehydrated polyvinyl alcohol or dehydrochlorinated polyvinyl chloride. Among them, a polarizing element containing a dichroic substance such as a polyvinyl alcohol-based film and iodine is preferable. The thickness of the polarizing elements is not particularly limited, and is generally 2-25 μm.

A polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretched it can be produced, for example, by immersing a polyvinyl alcohol-based film in an aqueous solution of iodine for dyeing and stretching it To 3 to 7 times the original length. It can also be immersed in boric acid or potassium iodide that may contain zinc sulfate, zinc chloride, etc., as needed. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water for washing before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt or anti-blocking agent on the surface of the polyvinyl alcohol-based film can be washed away. In addition, by swelling the polyvinyl alcohol-based film, it can also prevent uneven dyeing. Uniform effect. Stretching may be performed after dyeing with iodine, or stretching may be performed while dyeing one side, or dyeing with iodine may be performed after stretching. It can be extended in aqueous solutions or water baths such as boric acid or potassium iodide.

<Adhesive layer> The adhesive layer used in the present invention includes a base polymer and polysiloxane oligomer Ps.

The adhesive constituting the adhesive layer used in the present invention is not particularly limited, and rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyls can be used. Ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. Various base polymers can be used according to the adhesive used.

Among the above-mentioned adhesives, it is preferable to use those that are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive properties, and are excellent in weather resistance or heat resistance. As those exhibiting such characteristics, acrylic adhesives are preferably used. As the base polymer of the acrylic adhesive, a (meth)acrylic polymer is used. Furthermore, (meth)acrylate includes acrylate and/or methacrylate.

<Base polymer> In the present invention, as the base polymer, a (meth)acrylic polymer is generally used.

(1) Alkyl (meth)acrylate (A) The (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a monomer unit as a main component. As the (meth)acrylic acid alkyl ester (A) constituting the main skeleton of the (meth)acrylic polymer, a linear or branched C1-C20 alkyl (meth)acrylate can be used. Examples of C1-C20 alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth) ) Amyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Alkyl ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (meth)acrylate Base) hexadecyl acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nineteen (meth)acrylate Alkyl ester, eicosyl (meth)acrylate, etc. are not limited to these. These alkyl (meth)acrylates can be used alone or in combination.

In one embodiment of the present invention, the (meth)acrylic polymer may preferably contain one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as monomer units . Examples of other alkyl (meth)acrylates that can be preferably used as monomer units of (meth)acrylic polymers include: methyl acrylate, methyl methacrylate (MMA), methyl N-Butyl acrylate (BMA), 2-ethylhexyl methacrylate (2EHMA), etc.

In one embodiment of the present invention, the homopolymer of the alkyl (meth)acrylate (A) used as the monomer unit of the base polymer has a glass transition temperature of -80°C or more and 0°C or less. The glass transition temperature of the homopolymer of the alkyl (meth)acrylate (A) is preferably -70°C to -5°C, more preferably -60°C to -10°C.

In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as the monomer unit of the base polymer may contain more than 80% by weight based on the weight of the base polymer. The alkyl (meth)acrylate (A) is based on the weight of the base polymer, preferably 85% by weight or more, and more preferably 90% by weight or more.

In a preferred embodiment of the present invention, the homopolymer may contain alkyl (meth)acrylate (A) with a glass transition temperature of -60°C or more and 0°C or less as the monomer of the base polymer. unit.

In one embodiment of the present invention, the (meth)acrylic polymer not only contains alkyl (meth)acrylate (A) as the main component, but also may further include alkyl (meth)acrylate as necessary. Other monomers for ester copolymerization (copolymerizable monomers). As the copolymerizable monomer, a monomer having a polar group (for example, a carboxyl group, a hydroxyl group, a ring containing a nitrogen atom, etc.) can be preferably used. Monomers with polar groups can be beneficial to introduce cross-linking points to acrylic polymers, or to improve the cohesion of (meth)acrylic polymers. The copolymerizable monomer can be used alone or in combination of two or more.

As non-limiting specific examples of copolymerizable monomers, examples include: carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, sulfonic acid group or phosphoric acid group-containing monomers, epoxy group-containing monomers, Cyano monomers, isocyanate group-containing monomers, amine group-containing monomers, monomers with a nitrogen atom-containing ring, monomers with a succinimide skeleton, maleimines, Ikon imines, aminoalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, (Meth)acrylates of alicyclic hydrocarbon groups, (meth)acrylates having aromatic hydrocarbon groups, in addition to (meth)acrylates containing heterocyclic rings such as methyl tetrahydrofuran (meth)acrylate, and chlorine-containing Halogen-containing (meth)acrylates such as ethylene or fluorine atom (meth)acrylates, polysiloxane (meth)acrylates and other silicon-containing (meth)acrylates, derivatives of terpene compounds (Meth)acrylate obtained from alcohol.

Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc.; Examples of acid anhydride group-containing monomers include maleic anhydride and itaconic anhydride; examples of hydroxyl-containing monomers include: 2-hydroxyethyl (meth)acrylate and 2-hydroxy (meth)acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (methyl) ) 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc. ) Hydroxyalkyl acrylate, etc.; as monomers containing sulfonic acid or phosphoric acid groups, for example, styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2-(meth)acrylamide -2-Methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)acrylic acid sulfopropyl ester, (meth)acryloxynaphthalenesulfonic acid, phosphoric acid 2-hydroxyethylacrylamide As the epoxy-containing monomers, for example, glycidyl (meth)acrylate or 2-ethyl glycidyl (meth)acrylate and other epoxy-containing acrylates, allyl Glycidyl ether, (meth)acrylic acid glycidyl ether, etc.; as cyano group-containing monomers, for example, acrylonitrile, methacrylonitrile, etc.; as isocyanate group-containing monomers, for example: (methyl ) 2-isocyanatoethyl acrylate, etc.; as the amine group-containing monomer, for example, (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N -Diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-bis(normal) Butyl)(meth)acrylamide, N,N-di(tert-butyl)(meth)acrylamide, etc. N,N-dialkyl(meth)acrylamide; N-ethyl( (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-butyl (meth) acrylamide and other N-alkyl ( (Meth)acrylamide; N-vinylcarboxamides such as N-vinylacetamide; Other examples include: N,N-dimethylaminopropyl(meth)acrylamide, hydroxyethyl Acrylamide, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methylolpropane (meth)acrylamide, N-methoxymethyl (Meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-(meth)acrylamide, etc. ; As a monomer with a ring containing nitrogen atoms, for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone , N-vinylpyrimidine, N-vinylpiperidine, N-vinylpyrrole, N-vinylpyrrole, N- Vinyl imidazole, N-vinyl azole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine , N-vinyl 𠰌line, N-vinyl-3-𠰌 linone, N-vinyl-2-caprolactone, N-vinyl-1,3-㗁𠯤-2-one, N-ethylene Group-3,5-𠰌linedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, N-vinylpyrazole, etc. (for example, N -Vinyl-2-caprolactam and other internal amines); as a monomer having a succinimide skeleton, for example, N-(meth)acryloxymethylene succinylidene Amine, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, etc. ; As maleimines, for example, N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide Amines, N-phenyl maleimines, etc.; as the iconimines, for example, N-methyl iconimines, N-ethyl iconimines, N-butyl Ikonimines, N-octyl Ikonimines, N-2-Ethylhexyl Ikonimines, N-Cyclohexyl Ikonimines, N-Lauryl Ikonimines, etc. ; As aminoalkyl (meth)acrylates, for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylic acid N,N-Diethylaminoethyl, (meth)acrylic acid tertiary butylaminoethyl; as (meth)acrylic acid alkoxyalkyl esters, for example: (meth)acrylate methyl Oxyethyl, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, etc.; Examples of vinyl esters include vinyl acetate, vinyl propionate, etc.; examples of vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether; as aromatic vinyl compounds Examples include: styrene, α-methylstyrene, vinyl toluene, etc.; as olefins, for example, ethylene, butadiene, isoprene, isobutylene, etc.; as those with alicyclic hydrocarbon group ( Meth) acrylate, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isopropyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc.; The (meth)acrylate of the aromatic hydrocarbon group includes, for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.

In the case of using such a copolymerizable monomer, the amount used is not particularly limited, and it is usually suitably set to 0.01% by weight or more of the total monomer component. From the viewpoint of better exerting the effect obtained by using the copolymerizable monomer, the usage amount of the copolymerizable monomer can be set to 0.1% by weight or more of the total monomer component, or 1% by weight or more. In addition, the usage amount of the copolymerizable monomer can be set to 50% by weight or less of the total amount of monomer components, preferably 40% by weight or less. Thereby, the cohesive force of the adhesive can be prevented from being too high, and the tactile feel at normal temperature (25°C) can be improved.

In one embodiment of the present invention, the (meth)acrylic polymer contains the alkyl (meth)acrylate as the main component, and optionally the hydroxyl-containing monomer as described above (typically hydroxyl-containing (Meth)acrylic monomer) as the monomer unit. As the hydroxyl group-containing monomer, as described above, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate Esters, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc. (meth)hydroxyalkyl acrylates, etc., (meth) 2-hydroxyethyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. Among them, preferred examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA). By using hydroxyl-containing monomers, the cohesive force or polarity of the adhesive can be adjusted to improve the adhesive force after heating. In addition, the hydroxyl-containing monomer improves the hydrophilicity of the adhesive layer and can also be beneficial in suppressing the decrease in transparency caused by moisture. In the case of containing hydroxyl-containing monomers, the amount of hydroxyl-containing monomers used is not particularly limited, and is usually based on the total amount of monomer units used to prepare the (meth)acrylic polymer, for example, it can be set to 0.01 weight % Or more, 0.1% by weight or more, 0.5% by weight or more, etc.

In addition, in one embodiment of the present invention, the (meth)acrylic polymer contains alkyl (meth)acrylate as the main component, and may also contain multifunctional monomers as necessary for the adhesive layer. Cohesion adjustment, etc. Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate )Acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, four Hydroxymethylmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylic Ester, butanediol (meth)acrylate, hexanediol di(meth)acrylate, etc. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types. The amount of polyfunctional monomer used varies according to its molecular weight or number of functional groups, etc. It is usually set to 0.01% by weight to 3.0 with respect to the total amount of monomer components used to prepare alkyl (meth)acrylate (A) The range of% by weight can be set to 0.02% to 2.0% by weight, or 0.03% to 1.0% by weight.

(2) Polar monomer (B) In one embodiment of the present invention, the base polymer may further include at least one selected from the group consisting of carboxyl group-containing monomer (b1) and nitrogen-containing monomer (b2) The polar monomer (B) serves as a copolymerizable monomer unit.

In one embodiment of the present invention, the above-mentioned polar monomer (B) may contain 0-20% by weight based on the weight of the base polymer. The polar monomer (B) is based on the weight of the base polymer, preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight.

(2-1) Carboxyl group-containing monomer (b1) In the present invention, the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit. Examples of the carboxyl group-containing monomer (b1) include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isobutylene. Acid etc., but not limited to these. In a preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) can be acrylic acid or methacrylic acid. In a more preferable embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid (AA).

(2-2) Nitrogen-containing monomer (b2) In the present invention, the base polymer may contain a nitrogen-containing monomer (b2) as a copolymerizable monomer unit. Examples of the nitrogen-containing monomer (b2) include: vinyl monomers having an internal amide ring (for example, vinyl pyrrolidone monomers such as N-vinylpyrrolidone and methyl vinylpyrrolidone) , And a vinyl lactam-based monomer having an inner amido ring such as β-lactam ring, δ-lactam ring, and ε-lactam ring, etc.); maleimide, N -Cyclohexyl maleimide, N-phenyl maleimide and other maleimide monomers; (meth)acrylamide, N,N-dimethyl ( Meth) acrylamide, N,N-diethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl ( Meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol propane (meth) acrylamide, etc. (N-substituted ) Amido monomers; (meth)aminoethyl acrylate, (meth)aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid aminoalkyl ester monomers such as tributylaminoethyl and 3-(3-pyridyl)propyl (meth)acrylate; N-(meth)acryloxymethylene N-(meth)acryloyl-6-oxyhexamethylene-succinimide, N-(meth)acryloyl-8-oxyoctamethylene-butane Diamide and other succinimide monomers; cyano (meth)acrylate monomers such as acrylonitrile and methacrylonitrile; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl Piperidine, vinylpyrrole, vinylpyrrole, vinylimidazole, vinyloxazole, vinylpyrroline, N-vinylcarboxamides, etc.; but not limited to these. In a preferred embodiment of the present invention, the nitrogen-containing monomer (b2) can be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferable embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.

The method for obtaining the (meth)acrylic polymer is not particularly limited, and the solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, photopolymerization method, etc. can be suitably used as the synthesis method of acrylic polymer. Various polymerization methods are well known. Among several aspects, the solution polymerization method can be preferably used. The polymerization temperature during solution polymerization can be appropriately selected according to the types of monomers and solvents used, the types of polymerization initiators, etc., for example, it can be set at about 20°C to 170°C (typically about 40°C to 140°C).

The initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators or photopolymerization initiators, etc. according to the polymerization method. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

As the thermal polymerization initiator, for example, an azo polymerization initiator (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2 ,2'-Azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-Amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane) dihydrochloride, 2,2'- Azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethylisobutylamidine) dihydrochloride, etc.); potassium persulfate, etc. Sulfate; peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl maleate, lauric peroxide, etc.); redox-based polymerization initiator, etc. The amount of the thermal polymerization initiator used is not particularly limited. For example, relative to 100 parts by weight of the monomer components used to prepare the acrylic polymer, it can be 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 3 parts by weight. Amount within the range of parts by weight.

系光聚合起始劑、醯基氧化膦系光聚合起始劑等。光聚合起始劑之使用量並無特別限制，例如相對於用以製備丙烯酸系聚合物之單體成分100重量份，可設為0.01重量份～5重量份，較佳為0.05重量份～3重量份之範圍內之量。The photopolymerization initiator is not particularly limited. For example, benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α-ketol-based photopolymerization initiator, and aromatic sulfonate can be used. Chlorine-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzil-based photopolymerization initiators, benzophenone-based photopolymerization initiators, Ketal photopolymerization initiator, 9-oxysulfur 𠮿

It is a photopolymerization initiator, an oxyphosphine oxide photopolymerization initiator, etc. The amount of the photopolymerization initiator used is not particularly limited. For example, it can be 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, relative to 100 parts by weight of the monomer components used to prepare the acrylic polymer. Amount within the range of parts by weight.

In one embodiment of the present invention, the (meth)acrylic polymer may be in a mixture prepared with a polymerization initiator in the monomer components as described above, for example, ethyl acetate, toluene, etc. may be used for polymerization. The solvent obtains a (meth)acrylic polymer by solution polymerization. As an example of solution polymerization, the reaction is performed by adding a polymerization initiator under an inert gas flow such as nitrogen, and is usually carried out under reaction conditions of about 50 to 70°C for about 5 to 30 hours. The adhesive layer disclosed in this specification can be formed using, for example, an adhesive composition containing the above-mentioned (meth)acrylic polymer, the following polysiloxane oligomer Ps, and other additives.

In the present invention, the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2.5 million. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer may preferably be 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.

<Polysiloxane oligomer Ps> In the present invention, the adhesive layer includes polysiloxane oligomer Ps. Polysiloxane oligomer Ps, due to the low polarity and mobility of the siloxane structure, can function as a delay agent for increasing the adhesion force which helps suppress the initial adhesion and increase the adhesion force increase ratio. As the polysiloxane oligomer Ps, it can be preferably used for polymers having a siloxane structure in the side chain.

The glass transition temperature (Tg) of the polysiloxane oligomer Ps used in the present invention is in the range of -50°C to 100°C. In one embodiment of the present invention, the Tg of the polysiloxane oligomer Ps is preferably -30°C or higher and 70°C or lower, more preferably -20°C or higher and 60°C or lower. If the Tg of the polysiloxane oligomer Ps is within the above range, it can achieve a high level of both initial low adhesion and increased adhesion during use (strong adhesion).

The polysiloxane oligomer Ps used in the present invention has a weight average molecular weight Mw in the range of 10,000 to 300,000. In one embodiment of the present invention, the weight average molecular weight Mw of the polysiloxane oligomer Ps is preferably 12,500 or more and 2,500,000 or less, more preferably 15,000 or more and 2,000,000 or less. If the weight average molecular weight Mw of the polysiloxane oligomer Ps is within the above range, it is easy to adjust the compatibility or mobility in the adhesive layer to an appropriate range, so that it is easy to achieve a high level of both initial low adhesion Adhesive sheet with strong adhesiveness when used.

In a preferred embodiment of the present invention, the Tg of the polysiloxane oligomer Ps is above -70°C and below 30°C, the polysiloxane functional group equivalent of the side chain is 1000 to 20000 g/mol, and the weight average molecular weight Mw can be Above 10,000 and below 300,000.

In one embodiment of the present invention, the polysiloxane oligomer Ps may include monomers S1 with a polyorganosiloxane skeleton, and monomers whose glass transition temperature of the homopolymer is above -70°C and below 180°C. Monomer unit.

(1) The monomer S1 with polyorganosiloxane skeleton can be used in the polysiloxane oligomer Ps of the present invention. The monomer S1 with polyorganosiloxane skeleton is not particularly limited, and polyorganosiloxane can be used. Any monomer of alkane skeleton. As the polyorganosiloxane skeleton, for example, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), etc., but not limited In these.

[化2]

其中，上述通式(1)、(2)中之R³ 為氫或甲基，R⁴ 為甲基或1價有機基，m及n為0以上之整數。As the monomer S1 having a polyorganosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as single-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., examples include: X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X- 22-174BX, X-22-2404, etc. The monomer S1 having a polyorganosiloxane skeleton can be used alone or in combination of two or more. [化1]

[化2]

Among them, R ³ in the above general formulas (1) and (2) is hydrogen or a methyl group, R ⁴ is a methyl group or a monovalent organic group, and m and n are integers of 0 or more.

The polysiloxane functional group equivalent of the side chain of the polysiloxane oligomer Ps used in the present invention is 1,000 to 20,000 g/mol. In one embodiment of the present invention, the polysiloxane functional group equivalent of the side chain of the polysiloxane oligomer Ps is preferably 1200-18000 g/mol, more preferably 1500-15000 g/mol. If the polysiloxane functional group equivalent of the side chain of the polysiloxane oligomer Ps is within the above range, it is easy to adjust the compatibility (for example, compatibility with the base polymer) or mobility in the adhesive layer To a moderate range, it is easy to realize an adhesive sheet with a high level of low initial adhesiveness and strong adhesiveness during use.

Here, "functional group equivalent" refers to the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. Regarding the labeling unit g/mol, it is converted to 1 mol of the functional group. The functional group equivalent of the monomer S1 having a polyorganosiloxane skeleton can be calculated from, for example, ¹ H-NMR (proton NMR) spectral intensity based on nuclear magnetic resonance (NMR). The calculation of the functional group equivalent (g/mol) of the monomer S1 with a polyorganosiloxane skeleton based on ¹ H-NMR spectrum intensity can be performed based on the general structure analysis method of ¹ H-NMR spectrum analysis, if necessary Refer to the description in Japanese Patent No. 5951153.

Furthermore, when two or more monomers with different functional group equivalents are used as the monomer S1 having a polyorganosiloxane skeleton, as the functional group equivalent of the monomer S1, an arithmetic average can be used. That is, the functional group equivalent of monomer S1 including n types of monomers (monomer S1 ₁ , monomer S1 ₂ ... monomer S1 _n ) with different functional group equivalents can be calculated by the following formula. S1 functional group equivalent of the monomer (g / mol) = (amount of formulation _{S1. 1. 1} of the monomer having a functional group equivalent S1 × S1 monomer ₂ + monomer having a functional group equivalent of the monomer blending amount × S1 + ... + ₂ of Sl blending amount of the functional group equivalent of _n × _n monomers of monomer S1) / (S1 ₁ formulations of the monomer amount of the monomer formulation + S1 ₂ + ... + the amount of the monomer formulation of Sl _n)

The content of the monomer S1 having a polyorganosiloxane skeleton relative to all the monomer components used to prepare the polysiloxane oligomer Ps, for example, can be 5% by weight or more, and it can better serve as a retarder for increasing adhesion From the viewpoint of the effect, it is preferably 10% by weight or more, and 15% by weight or more. In some aspects, the content of the above-mentioned monomer S1 may be 20% by weight or more, for example. In addition, the content of the monomer S1 having a polyorganosiloxane skeleton is preferably set to 60 from the viewpoint of polymerization reactivity or compatibility with respect to all monomer components used to prepare the polysiloxane oligomer Ps. The weight% or less may be 50 weight% or less, 40 weight% or less, or 30 weight% or less. If the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize an adhesive sheet that has a high level of low initial adhesiveness and increased adhesive force during use (strong adhesiveness).

(2) Monomers with a homopolymer glass transition temperature of -70°C or higher and 180°C or lower. The polysiloxane oligomer Ps of the present invention includes (A) which can be copolymerized with the aforementioned monomer S1 having a polyorganosiloxane skeleton. Base) acrylic monomers or other copolymerizable monomers. As the copolymerizable (meth)acrylic monomers or other copolymerizable monomers that can be used in the silicone oligomer Ps of the present invention, homopolymers can be used. The glass transition temperature is -70°C or more and 180°C or less Examples of the monomer include alkyl (meth)acrylate and (meth)acrylate having an alicyclic hydrocarbon group, but are not limited to these. Examples of (meth)acrylic acid alkyl esters include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), and butyl acrylate ( BA), 2-ethylhexyl acrylate (2-EHA). Examples of (meth)acrylates having alicyclic hydrocarbon groups include: 2-((3-hydroxymethyl)-adamantane methacrylate -1-yl) methoxy-2-oxoethyl ester (2EHAMA), cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, iso-(meth)acrylate, (meth) (Yl) biscyclopentyl acrylate, 1-adamantyl (meth)acrylate, etc., but not limited to these. In one embodiment of the present invention, it may contain 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), and At least one of iso-(IBXMA) methacrylate (IBXMA) is used as a monomer unit. In another embodiment of the present invention, at least one selected from the group consisting of dicyclopentyl methacrylate, isopropyl methacrylate, and cyclohexyl methacrylate may be contained as a monomer unit. These monomers can be used individually by 1 type or in combination of 2 or more types.

The usage amount of the above-mentioned alkyl (meth)acrylate and the above-mentioned (meth)acrylate having alicyclic hydrocarbon group relative to all monomer components used to prepare polysiloxane oligomer Ps can be, for example, 10% by weight Above 95% by weight, can be 20% by weight to 95% by weight, can be 30% by weight to 90% by weight, can be 40% by weight to 90% by weight, or can be 50% by weight to 85% by weight .

Regarding another example of the monomer that can be included together with the monomer S1 as the monomer unit constituting the polysiloxane oligomer Ps, the following can be cited as the monomer that can be used for the alkyl (meth)acrylate (A) Examples of carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, isocyanate group-containing monomers, amide group-containing monomers, Nitrogen ring monomers, monomers with succinimide skeleton, maleimides, iconimines, aminoalkyl (meth)acrylates, vinyl esters , Vinyl ethers, olefins, (meth)acrylates with aromatic hydrocarbon groups, (meth)acrylates containing heterocycles, (meth)acrylates containing halogen atoms, derived from terpene compound derivative alcohols The (meth)acrylate and so on.

Regarding another example of the monomer that can be included together with the monomer S1 as the monomer unit constituting the polysiloxane oligomer Ps, examples include: ethylene glycol bis(meth)acrylate, diethylene glycol bis(formaldehyde) Base) acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol Oxyalkylene di(meth)acrylates such as di(meth)acrylate; at the end of the polyoxyalkylene chain of monomers with a polyoxyalkylene skeleton, such as polyethylene glycol or polypropylene glycol It has polymerizable functional groups such as (meth)acrylic acid groups, vinyl groups, and allyl groups, and has an ether structure (alkyl ether, aryl ether, aralkyl ether, etc.) at the other end. Alkyl ether; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, (meth) (Meth)acrylic acid alkoxyalkyl esters such as ethoxypropyl acrylate; (meth)acrylic acid alkali metal salts and other salts; trimethylolpropane tri(meth)acrylate and other poly(meth) Acrylate; vinylidene chloride, 2-chloroethyl (meth)acrylate and other halogenated vinyl compounds; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazole Oxazoline group-containing monomers such as morpholine, 2-isopropenyl-2-oxazoline; (meth)acryloyl aziridine, (meth)acrylic acid-2-aziridinyl ethyl ester, etc. containing nitrogen Propidinyl monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, adducts of lactones and 2-hydroxyethyl (meth)acrylate, etc. Hydroxy-containing vinyl monomers; fluorine-containing vinyl monomers such as fluorine-substituted alkyl (meth)acrylate; 2-chloroethyl vinyl ether, vinyl monochloroacetate and other reactive halogen-containing vinyl monomers; Vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethane Organosilicon-containing vinyl monomers such as oxytrimethoxysilane; in addition, macromonomers with radical polymerizable vinyl groups at the end of monomers formed by polymerizing vinyl groups can be listed. These can be copolymerized with the monomer S1 alone or in combination with the monomer S1.

In the case where the monomer component used to prepare the polysiloxane oligomer Ps includes the monomer S1 and the (meth)acrylic monomer, the monomer S1 and the (meth)acrylic monomer are in the above monomer component The total amount in the whole can be, for example, 50% by weight or more, 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight %.

The composition of the (meth)acrylic monomer contained in the aforementioned monomer component can be set, for example, in such a way that the glass transition temperature T _m1 based on the composition of the (meth)acrylic monomer is higher than 0°C. Here, the glass transition temperature T _m1 based on the composition of the (meth)acrylic monomer refers to the composition based only on the (meth)acrylic monomer in the monomer components used to prepare the polysiloxane oligomer Ps , Use the formula of Fox to find the Tg. T _m1 can only be the (meth)acrylic monomer in the monomer component used to prepare the polysiloxane oligomer Ps. Applying the formula of the above Fox, it is determined from the average of each (meth)acrylic monomer The glass transition temperature of the polymer and the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer are calculated. If a polysiloxy oligomer Ps with a glass transition temperature T _m1 higher than 0°C is used, it is easy to suppress the initial adhesion. In addition, by using polysiloxane oligomer Ps with a glass transition temperature T _m1 higher than 0°C, it is easy to obtain an adhesive sheet with a relatively large increase in adhesion.

In some aspects, T _m1 may be -20°C or higher, may be -10°C or higher, may be 0°C or higher, or may be 10°C or higher. If T _m1 becomes higher, there is a tendency that the initial adhesion force of the attachment is generally better suppressed. In addition, T _m1 may be, for example, 90°C or lower, 80°C or lower, 70°C or lower, or less than 70°C. If T _m1 becomes lower, there is a tendency that the adhesive force tends to increase due to heating. The technology disclosed herein can be preferably implemented using polysiloxane oligomer Ps whose T _{m1 is} in the range of -20°C to 90°C or -10°C to 80°C, or 0°C to 70°C.

The polysiloxane oligomer Ps can be produced by, for example, polymerizing the aforementioned monomers by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method.

In order to adjust the molecular weight of the polysiloxane oligomer Ps, a chain transfer agent can be used. Examples of chain transfer agents used include: octyl mercaptan, lauryl mercaptan, tertiary nonyl mercaptan, tertiary dodecane mercaptan, mercaptoethanol, α-thioglycerol, and other compounds having mercapto groups; mercaptoacetic acid , Methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, tertiary butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, thioglycolic acid Decyl ester, lauryl thioglycolate, thioglycolate of ethylene glycol, thioglycolate of neopentyl glycol, thioglycolate of pentaerythritol, etc.; α-methylstyrene dimerization Things etc.

The amount of the chain transfer agent used is not particularly limited. It is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.2, relative to 100 parts by weight of the monomer. Parts by weight ~ 10 parts by weight. By adjusting the addition amount of the chain transfer agent in this way, a polysiloxane oligomer Ps with a suitable molecular weight can be obtained. In addition, a chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

In an embodiment of the present invention, the polysiloxane oligomer Ps may contain 0.1 to 20 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. In the embodiment of the present invention, the polysiloxane oligomer Ps may preferably contain 0.25 to 10 parts by weight, more preferably 0.5 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. Copies. If the content of the silicone oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed, and a higher adhesive force after heating can be obtained.

Furthermore, the polysiloxane oligomer Ps as described above can function as a retarder for increasing the adhesion force by being formulated in the adhesive layer. The adhesive sheet disclosed herein can be preferably implemented in the following manner, that is, the adhesive constituting the adhesive layer includes a base polymer and an adhesion increase retarder, and the adhesion increase retarder includes a silicone oligomer Ps . It is believed here that the reason why the polysiloxane oligomer Ps functions as an adhesive force increase retardant is that the adhesive sheet that exists on the surface of the adhesive layer is used in the adhesive sheet before the adherence to the adherend. The silicone oligomer Ps suppresses the initial adhesion, and the adhesive flows through time or heating after being attached, thereby reducing the amount of the silicone oligomer Ps on the surface of the adhesive layer, and the silicone The oxygen oligomer Ps is compatible with the adhesive, and the adhesive force increases. Therefore, as the above-mentioned adhesion strength increase retarder in the technology disclosed herein, other materials that can perform the same function can be used instead of polysiloxane oligomer Ps or combined with polysiloxane oligomer Ps. As a non-limiting example of such a material, a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as "polymer Po") can be cited. The polymer Po may be, for example, a polymer containing monomer units derived from a monomer having a polyoxyalkylene skeleton. As a specific example, any single polymer or copolymer of two or more types of monomers having a polyoxyalkylene skeleton as described above, one or two types of monomers having a polyoxyalkylene skeleton can be used The above-mentioned copolymers with other monomers (for example, (meth)acrylic monomers) are used as polymer Po. The usage amount of the monomer having a polyoxyalkylene skeleton is not particularly limited. For example, the usage amount of the monomer S1 in the above polysiloxane oligomer Ps can also be applied to the polyoxyalkylene in the polymer Po. The amount of monomer used in the base skeleton. In addition, the amount of the polymer Po used in the adhesive layer is not particularly limited. For example, the amount of the polysiloxane oligomer Ps relative to the base polymer can also be applied to the use of the polymer Po relative to the base polymer. the amount. Alternatively, a part of the amount of the above-mentioned polysiloxane oligomer Ps relative to the base polymer (for example, about 5% to 95% by weight of the total amount of polysiloxane oligomer Ps, or 15 Weight% to 85% by weight or about 30% to 70% by weight) is replaced with polymer Po.

In an embodiment of the present invention, the melting temperature of the polysiloxane oligomer Ps may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the polysiloxane oligomer Ps can be -10 to 90°C, 0 to 80°C.

<Other ingredients> (Crosslinking agent) For the adhesive layer disclosed in this specification, a crosslinking agent can be used for adjustment of cohesive force, etc. As the crosslinking agent, commonly used crosslinking agents can be used, such as epoxy crosslinking agents, isocyanate crosslinking agents, silicone crosslinking agents, azoline crosslinking agents, aziridine crosslinking agents Linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, metal chelate-based cross-linking agents, etc. In particular, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents can be preferably used. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

Specifically, examples of isocyanate-based crosslinking agents include: toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate Phenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and these and trimethylol Adducts of polyhydric alcohols such as propane. Or compounds having at least one isocyanate group and one or more unsaturated bonds in one molecule. Specifically, 2-isocyanatoethyl (meth)acrylate can also be used as isocyanate series Crosslinking agent. These can be used individually by 1 type or in combination of 2 or more types.

Examples of epoxy crosslinking agents include: bisphenol A, epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether Glyceryl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidol -M-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc. These can be used individually by 1 type or in combination of 2 or more types.

Regarding the metal chelate compound, examples of the metal component include aluminum, iron, tin, titanium, nickel, etc., and examples of the chelate component include acetylene, methyl acetylacetate, and ethyl lactate. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the crosslinking agent used can be, for example, 0.01 part by weight or more, preferably 0.05 part by weight or more with respect to 100 parts by weight of the base polymer. By increasing the amount of crosslinking agent used, there is a tendency to obtain higher cohesion. In some aspects, the usage amount of the crosslinking agent relative to 100 parts by weight of the base polymer may be 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more. On the other hand, from the viewpoint of avoiding the decrease in tackiness caused by excessively increasing the cohesive force, the usage amount of the crosslinking agent relative to 100 parts by weight of the base polymer is usually preferably set to 15 parts by weight or less, and can be set to 10 parts by weight or less It can also be set to 5 parts by weight or less. In adhesives composed of polysiloxane oligomer Ps or other adhesion increase retarders, if the amount of crosslinking agent used is not too much, the fluidity of the adhesive can be used to better show the effect of the adhesion increase retarder It can also be advantageous in terms of the viewpoint.

The technology disclosed in this specification can be preferably implemented by using at least an isocyanate-based crosslinking agent as the crosslinking agent. From the viewpoint of easily realizing an adhesive sheet with a higher cohesive force after heating and a relatively large increase in adhesive force, in some aspects, the usage amount of the isocyanate-based crosslinking agent relative to 100 parts by weight of the base polymer can be set to 5 Parts by weight or less may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, or 0.5 parts by weight or less.

In order to perform any of the above-mentioned crosslinking reactions more efficiently, a crosslinking catalyst may also be used. As the crosslinking catalyst, for example, a tin-based catalyst (especially dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst used is not particularly limited. For example, it can be approximately 0.0001 part by weight to 1 part by weight relative to 100 parts by weight of the base polymer.

(Silane coupling agent) The adhesive layer disclosed in this specification may further contain a silane coupling agent. By using silane coupling agent, durability can be improved. As the silane coupling agent, one having any appropriate functional group can be used. Specifically, as the functional group, for example, a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoxy group, an isocyanate group, a styryl group, and a polysulfide group can be mentioned. Base etc. Specifically, for example, vinyl-containing silane coupling agents such as vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, etc.; γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-ring Oxycyclohexyl) ethyl trimethoxysilane and other epoxy-containing silane coupling agents; γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N-(1,3-dimethylbutylene) Yl) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and other amine-containing silane coupling agents; γ-mercaptopropylmethyldimethoxysilane and other mercapto-containing silane coupling agents; Styryl trimethoxysilane and other styryl-containing silane coupling agents; γ-propylene oxypropyl trimethoxy silane, γ-methacryloxy propyl triethoxy silane, etc. containing (form Yl) acryl-based silane coupling agent; 3-isocyanatopropyl triethoxysilane and other isocyanate-containing silane coupling agents; bis(triethoxysilylpropyl) tetrasulfide, etc. Polysulfide-based silane coupling agent, etc. The silane coupling agent can preferably use, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, -Mercaptopropylmethyldimethoxysilane.

The above-mentioned silane coupling agent may be used alone, or two or more of them may be used in combination. The content as a whole relative to 100 parts by weight of the base polymer is preferably 0.001 to 5 parts by weight of the above-mentioned silane coupling agent, and more preferably 0.01 ~1 part by weight, more preferably 0.02 to 1 part by weight, and still more preferably 0.05 to 0.6 part by weight.

In addition, the adhesive layer in the technology disclosed herein may also contain an adhesive imparting agent, a leveling agent, a plasticizer, a softening agent, and a coloring agent (dye, pigment, etc.) as necessary within the range that does not significantly hinder the effect of the present invention. ), fillers, antistatic agents, anti-aging agents, ultraviolet absorbers, antioxidants, light stabilizers, preservatives and other well-known additives that can be used in adhesives.

(Formation of Adhesive Layer) As a method of forming the adhesive layer, for example, it can be produced by the following method: coating the above-mentioned adhesive composition on a stripped separator, etc., and drying and removing the polymerization solvent, etc. The adhesive layer is then transferred to the polarizing film; or the above-mentioned adhesive composition is applied to the polarizing film, and the polymerization solvent is dried and removed to form the adhesive layer on the polarizing film. Furthermore, when the adhesive is applied, one or more solvents other than the polymerization solvent can also be appropriately added.

As the release-treated separator, a silicone release liner is preferably used. In the step of applying the adhesive composition of the present invention on such a liner and drying it to form an adhesive layer, as a method of drying the adhesive, an appropriate method can be appropriately adopted according to the purpose. It is preferable to use a method of heating and drying the above-mentioned coated film. The heating and drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature in the above range, an adhesive with excellent adhesive properties can be obtained.

The drying time can be appropriately used for an appropriate time. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

In addition, an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various easy bonding treatments such as corona treatment and plasma treatment are performed. In addition, the surface of the adhesive layer can also be easily bonded.

As a method of forming the adhesive layer, various methods can be used. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating , Curtain coating, die lip coating, extrusion coating using die nozzle coater, etc.

The thickness of the adhesive layer is not particularly limited, and is, for example, about 1-100 μm. It is preferably 2 to 50 μm, more preferably 2 to 40 μm, and still more preferably 5 to 35 μm.

When the above-mentioned adhesive layer is exposed, a peel-off treated sheet (separator) can also be used to protect the adhesive layer until actual use.

Examples of the constituent materials of the separator include: plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabrics, nets, and foam sheets Appropriate sheets, such as metal foil, laminates, etc., are suitable for use in terms of surface smoothness.

The plastic film is not particularly limited as long as it is a film that can protect the adhesive layer. Examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, and polymethylpentene Film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. For the above-mentioned separators, mold release and antifouling treatments can be carried out by using silicone, fluorine, long-chain alkyl or fatty acid amide-based mold release agents, silica powder, etc.; or coating type , Kneading type, vapor deposition type and other antistatic treatments. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., on the surface of the separator, the peelability from the adhesive layer can be further improved.

Furthermore, the peeled-off sheet used in the production of the above-mentioned adhesive layer-attached polarizing film can be directly used as a separator for the adhesive layer-attached polarizing film, thereby simplifying the steps. [Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited by the examples shown below. In addition, the parts and% in each example are based on weight. The following unspecified room temperature storage conditions are 23℃65%RH.

In addition, the weight average molecular weight Mw of the following polymers was measured using a GPC (Gel Permeation Chromatograph) device (manufactured by Tosoh, HLC-8220GPC) under the following conditions, and was measured by polystyrene Calculated by ethylene conversion. ·Sample concentration: 0.2 wt% (Tetrahydrofuran (THF) solution) ·Sample injection volume: 10 μl ·Lluent: THF ·Flow rate: 0.6 ml/min ·Measurement temperature: 40℃

<Production of polarizing element> A polyvinyl alcohol film with a thickness of 75 μm with an average degree of polymerization of 2400 and a degree of saponification of 99.9 mol% is immersed in warm water at 30°C for 60 seconds to swell. Then, it was immersed in a 0.3% aqueous solution of iodine/potassium iodide (weight ratio=0.5/8) to extend it to 3.5 times and dye the film. After that, it was stretched in a borate aqueous solution at 65°C so that the total stretch magnification became 6 times. After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a PVA (polyvinyl alcohol)-based polarizing element (SP value 32.8, thickness 23 μm). The moisture content is 14% by weight.

<Production of transparent protective film> The easy-adhesive surface of the acrylic resin film (SP value 22.2) with a thickness of 40 μm and a moisture permeability of 60 g/m ² /24 h is used by corona treatment.

<Active energy line> As the active energy line, use: ・Ultraviolet irradiation device (metal halide lamp enclosed with gallium): Light HAMMER10 manufactured by Fusion UV Systems, Inc; ・Light bulb: V bulb; ・Peak illuminance: 1600 mW/ cm ² ; ・Cumulative irradiation amount is 1000/mJ/cm ² (wavelength 380～440 nm). Furthermore, the illuminance of the ultraviolet rays was measured using the Sola-Check system manufactured by Solarell.

、日本化藥公司製造)1.4份混合，並於50℃下攪拌1小時，從而獲得活性能量線硬化型接著劑。<Preparation of Active Energy Ray Curing Adhesive> 38.3 parts of N-hydroxyethyl acrylamide (SP value 29.6, homopolymer Tg 123°C, manufactured by Xingren) as a radical polymerizable compound (A) , Tripropylene glycol diacrylate (trade name: ARONIX M-220, SP value 19.0, homopolymer Tg 69°C, manufactured by Toagosei Co., Ltd.) as a radical polymerizable compound (B) 19.1 parts, as a radical polymerizable Compound (C) of acryloline (SP value 22.9, homopolymer Tg 150℃, manufactured by Xingren Company) 38.3 parts, and photopolymerization initiator (trade name: KAYACURE DETX-S, diethyl 9 -Oxysulfur

, Nippon Kayaku Corporation) 1.4 parts were mixed and stirred at 50°C for 1 hour to obtain an active energy ray hardening adhesive.

<Production of Polarizing Film A> After forming a 0.5 μm-thick urethane-based easy-adhesive layer on the acrylic resin film, an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb; intaglio) Number of rolls: 1000/inch, rotation speed 140%/relative linear speed), the active energy ray-curable adhesive is applied to the easy-adhesive layer so that the thickness of the adhesive layer becomes 0.5 μm. Then, the above-mentioned acrylic resin film was used as the transparent protective film on the visible side and the panel side to be bonded to both surfaces of the above-mentioned polarizing element via the above-mentioned adhesive using a rolling machine. Thereafter, the both sides of the laminated acrylic resin film were heated to 50° C. using IR heaters, and the above-mentioned ultraviolet rays were irradiated on both sides to cure the active energy ray-curable adhesive. Furthermore, it was dried with hot air at 70°C for 3 minutes to obtain a polarizing film A having a transparent protective film on both sides of the polarizing element (Table 1). It is carried out at a linear speed of 25 m/min. [Table 1] Polarizing film Polarizer Visual recognition side protective film Polarizing element Panel side protective film Polarizing film A Acrylic resin film 40 μm 23 μm Acrylic resin film 40 μm

<Preparation of Adhesive> (Preparation of Polymer Solution A) Combine 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.075 parts of 2-hydroxyethyl acrylate and 0.3 parts of 2,2'-azobisisobutyronitrile with ethyl acetate The ester is added together in a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device to prepare a solution. Then, the solution was stirred while blowing nitrogen gas into the solution, and reacted at 60°C for 4 hours to obtain a solution containing an acrylic polymer with a weight average Mw of 2.2 million. Furthermore, ethyl acetate was added to this acrylic polymer-containing solution, and the acrylic polymer solution A whose solid content concentration was adjusted to 30% was obtained.

With respect to 100 parts of the solid content of the above-mentioned acrylic polymer solution A, 0.6 parts of the crosslinking agent mainly composed of a compound having an isocyanate group (manufactured by Japan Polyurethane (Stock), Trade name "Coronate L"), and 0.075 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403") as a silane coupling agent to prepare an adhesive Agent polymer solution A.

(Preparation of polymer solution B) 94 parts of 2-ethylhexyl acrylate (2EHA), 6 parts of acrylic acid and 0.3 part of 2,2'-azobisisobutyronitrile and ethyl acetate were added to the cooling tube, Nitrogen gas is introduced into the reaction vessel of the pipe, thermometer and stirring device to prepare the solution. Then, the solution was stirred while blowing nitrogen gas into the solution, and reacted at 60°C for 4 hours to obtain a solution containing an acrylic polymer with a weight average molecular weight Mw of 2.2 million. Furthermore, ethyl acetate was added to this acrylic polymer-containing solution, and the acrylic polymer solution (B) whose solid content concentration was adjusted to 30% was obtained.

With respect to 100 parts of the solid content of the above acrylic polymer solution (B), 0.6 parts of the cross-linking agent mainly composed of a compound having an isocyanate group (Japanese polyurethane (stock) Manufacture, trade name "Coronate L"), and 0.075 parts of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403") as a silane coupling agent, thereby Prepare adhesive polymer solution B.

The compositions of acrylic polymer solution (A) (polymer A) and acrylic polymer solution (B) (polymer B) are shown in Table 2 below. [Table 2] Adhesive main agent Monomer composition of polymer solution Weight average molecular weight Crosslinking agent Silane coupling agent BA 2EHA AA 2HEA species content species content Polymer A 100 - 5 0.075 2.2 million Coronate L 0.6 phr KBM-403 0.075 phr Polymer B - 94 6 - 2.2 million Coronate L 0.6 phr KBM-403 0.075 phr

(Preparation of Polysiloxane Oligomer A) Put 100 parts of ethyl acetate, 40 parts of MMA, and n-butyl methacrylate into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a cooler, and a dropping funnel. (BMA) 20 parts, 2-ethylhexyl methacrylate (2EHMA) 20 parts, functional group equivalent of 900 g/mol containing polyorganosiloxane skeleton methacrylate monomer (trade name: X- 22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts, functional group equivalent of 4600 g/mol containing polyorganosiloxane skeleton methacrylate monomer (trade name: KF-2012, Shin-Etsu Chemical Co., Ltd.) Co., Ltd.) 11.3 parts and 0.2 parts of methyl thioglycolate as a chain transfer agent. Then, after stirring for 1 hour at 70°C under a nitrogen atmosphere, 0.2 part of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was put in, and reacted at 70°C for 2 hours, and then put 0.1 part of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was then allowed to react at 80°C for 3 hours. In this way, a solution of polysiloxane oligomer is obtained. The weight average molecular weight Mw of the polysiloxane oligomer is 18,000.

(Preparation of other polysiloxane oligomers B to F) Regarding polysiloxane oligomers B to F, the monomer composition and mass parts were changed to the constituent components described in Table 3. In addition, the The oxygen oligomer A was produced in the same manner.

[table 3] Reprocessing agent Oligomer composition MMA BMA 2EHMA BA 2EHA X-22-174ASX KF-2012 Si oligomer A 40 20 20 8.7 11.3 Si oligomer B 50 15 15 8.7 11.3 Si oligomer C 60 10 10 8.7 11.3 Si oligomer D 10 35 35 8.7 11.3 Si oligomer E 70 5 5 8.7 11.3 Si oligomer F twenty two 20 38 8.7 11.3

(Preparation of Adhesive Solution) 1 part of polysiloxane oligomer A was prepared into the adhesive polymer solution A prepared above to prepare the acrylic adhesive solution used in Example 1. In the same manner, the adhesive polymer solution and the silicone oligomer described in Table 4 below were used to prepare the acrylic adhesive solutions used in Examples 2-19.

(Production of polarizing film with adhesive layer) [Example 1] ~ [Example 19] Then, the above-mentioned acrylic adhesive solution was uniformly coated on the polyterephthalene treated with a silicone release agent The surface of the ethylene formate film (separator film) was dried in an air circulating constant temperature oven at 155°C for 2 minutes to form an adhesive layer with a thickness of 20 μm on the surface of the separator film. The spacer on which the adhesive layer is formed is moved to one side of the above-mentioned polarizing film to produce the polarizing film with the adhesive layer.

[Comparative Example 1] In Comparative Example 1, except for the polysiloxane oligomer A, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.

[Comparative Example 2] ~ [Comparative Example 5] In Comparative Examples 2 to 5, polysiloxane containing ether groups (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "modified polysiloxane oil KF-353" ) Instead of polysiloxane oligomer A, and changing the blending amount as shown in Table 4. Except for this, the adhesive layer-attached polarizing film was produced in the same manner as in Example 1.

[Reference Example 1] In Reference Example 1, another reprocessing enhancer (manufactured by Kaneka, trade name "SAT10") was used instead of polysiloxane oligomer A, and the blending amount was changed as shown in Figure 4, except Otherwise, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.

The adhesive layer-attached polarizing film obtained in the foregoing Examples 1 to 19, Comparative Examples 1 to 5, and Reference Example 1 was evaluated as follows. The results are shown in Table 4.

<Evaluation of durability> Peel off the separator film of the polarizing film (37 inches) with the adhesive layer, and use a laminating machine to bond it to alkali-free glass with a thickness of 0.7 mm (manufactured by Corning, EG-XG ). Then, autoclave treatment is performed at 50°C and 0.5 MPa for 15 minutes to make the above-mentioned polarizing film completely adhere to the alkali-free glass. Then, they were put into a heating oven (heating) at 80°C, and the following criteria were used to evaluate whether the polarizing plate peeled off after 500 hours. A: No peeling was observed at all. B: Foaming to an extent that cannot be visually confirmed is observed. C: Peeling is observed to an extent that cannot be visually confirmed. D: Small foaming or peeling that can be confirmed visually is observed. E: Obvious foaming or peeling is observed.

<Evaluation of Adhesion> (1) Measurement of Initial Adhesion Under a standard environment of 23°C and 50% RH, cut the polarizing film with the adhesive layer to be 120 mm in length × 25 mm in width, and take the result as sample. The sample was crimped on a 0.7 mm alkali-free glass plate (EG-XG, manufactured by Corning) by making a 2 kg roller back and forth once, and then the adhesive force of the sample was measured. Adhesive force is measured by using a tensile testing machine (Autograph SHIMAZU AG-1 10KN) to peel off the sample at a peeling angle of 90° and a peeling speed of 300 mm/min (N/25 mm, measuring length 80 mm) It is determined by measurement. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measurement value. Performed under 3 samples. The average value of them is shown in the column of "2 kg roller" in Table 4 as the initial adhesive force. In addition, the reworkability was judged on the basis of the adhesion level based on the following criteria. A: Below 4 N/25 mm, 90% reprocessing is successful. B: More than 4 N/25 mm and less than 5 N/25 mm, more than 80% successful reprocessing. C: More than 5 N/25 mm and less than 6 N/25 mm, more than 70% of successful reprocessing. D: More than 6 N/25 mm and less than 7 N/25 mm, the reprocessing succeeded more than 60%. E: If it exceeds 7 N/25 mm, the reprocessing fails more than 40%.

(2) Measurement of adhesion after heating Cut the produced polarizing film with adhesive layer to a length of 120 mm × a width of 25 mm, and use the obtained as a sample. The sample was attached to an alkali-free glass plate (EG-XG, manufactured by Corning Corporation) with a thickness of 0.7 mm using a laminating machine, and then autoclaved at 50°C and 5 atm for 15 minutes to make it completely adhered, and then measured The adhesion of the sample. Adhesive force is measured by using a tensile testing machine (Autograph SHIMAZU AG-1 10KN) to peel off the sample at a peeling angle of 90° and a peeling speed of 300 mm/min (N/25 mm, measuring length 80 mm) It is determined by measurement. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measurement value. Performed under 3 samples. In Table 4, "60℃×2 h" and "60℃×24 h" indicate the adhesive strength after being placed at 60℃ for 2 hours and 24 hours, respectively.

[Table 4] Adhesive Reprocessing agent Glass transition temperature Tg Melting temperature Weight average molecular weight Si functional group amount g/mol content Adhesion of alkali-free glass Reprocessing Durability 2 kg roll 60℃×2 h 60℃×24 h No alkali No alkali Example 1 Polymer A Si oligomer A 47 53 18000 2990 0.5 phr 5.7 7.5 13.6 C A Example 2 Polymer A Si oligomer A 47 53 18000 2990 1.0 phr 4.8 8.7 12.1 B A Example 3 Polymer A Si oligomer A 47 53 18000 2990 2.0 phr 4.5 8.1 11.0 B A Example 4 Polymer A Si oligomer A 47 53 18000 2990 5.0 phr 3.9 7.8 10.1 A C Example 5 Polymer A Si oligomer B 60 64 18000 2990 0.5 phr 5.8 8.8 14.1 D A Example 6 Polymer A Si oligomer B 60 64 18000 2990 1.0 phr 4.8 8.7 13.0 B A Example 7 Polymer A Si oligomer B 60 64 18000 2990 2.0 phr 3.9 9.5 12.0 A A Example 8 Polymer A Si oligomer B 60 64 18000 2990 5.0 phr 2.2 9.2 10.1 A C Example 9 Polymer A Si oligomer C 73 77 18000 2990 0.5 phr 5.8 10.3 15.5 D A Example 10 Polymer A Si oligomer C 73 77 18000 2990 1.0 phr 51 11.4 15.8 C A Example 11 Polymer A Si oligomer C 73 77 18000 2990 2.0 phr 2.7 9.7 13.5 A A Example 12 Polymer A Si oligomer C 73 77 18000 2990 5.0 phr 1.1 5.5 7.2 A D Example 13 Polymer A Si oligomer D 14 twenty one 18000 2990 1.0 phr 4.9 9.2 11.9 B A Example 14 Polymer A Si oligomer D 14 twenty one 18000 2990 2.0 phr 3.5 8.5 11.0 A A Example 15 Polymer A Si oligomer E 89 93 19000 2990 1.0 phr 3.9 9.1 11.9 A A Example 16 Polymer A Si oligomer E 89 93 19000 2990 2.0 phr 1.3 5.4 7.2 A D Example 17 Polymer B Si oligomer A 47 53 18000 2990 1.0 phr 2.2 10.1 9.6 A D Example 18 Polymer A Si oligomer F -35 -31 18000 2990 1.0 phr 5.0 7.6 10.9 C B Example 19 Polymer A Si oligomer F -35 -31 18000 2990 2.0 phr 4.6 7.3 9.1 B D Comparative example 1 Polymer A - - - - - - 7.6 10.9 15.5 E A Comparative example 2 Polymer A KF-353 - - 7700 Non-reactive 0.5 phr 1.8 2.5 5.9 A E Comparative example 3 Polymer A KF-353 - - 7700 Non-reactive 1.0 phr 0.8 1.6 4.8 A E Comparative example 4 Polymer A KF-353 - - 7700 Non-reactive 2.0 phr 0.3 1.4 5.1 A E Comparative example 5 Polymer A KF-353 - - 7700 Non-reactive 5.0 phr 0.3 1.8 6.1 A E Reference example 1 Polymer A SAT10 - - 6000 1.0 phr 5.1 7.5 10.9 C C

As described above, according to the present invention, it is possible to provide a polarizing film with an adhesive layer that has both high durability and reworkability.

1: Polarizing element 2: Protective film 2': Protective film 3: Polarizing film 4: Adhesive layer 5: spacer 10: Polarizing film with adhesive layer

FIG. 1 is an example of a schematic cross-sectional view of the polarizing film with an adhesive layer of the present invention.

1: Polarizing element

2: Protective film

2': Protective film

3: Polarizing film

4: Adhesive layer

5: spacer

10: Polarizing film with adhesive layer

Claims (6)

A polarizing film with an adhesive layer, which is provided with a polarizing film and an adhesive layer, and the adhesive layer includes a base polymer and a polysiloxane oligomer Ps, and the base polymer is a (meth)acrylic polymer The above-mentioned polysiloxane oligomer Ps contains 0.1-20 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer, and the Tg of the above-mentioned polysiloxane oligomer Ps is above -50°C and below 100°C. The polysiloxy functional group equivalent of the chain is 1,000 to 20,000 g/mol, and the weight average molecular weight Mw is 10,000 to 300,000. The polarizing film with adhesive layer of claim 1, wherein the polysiloxane oligomer Ps includes monomer S1 having a polyorganosiloxane skeleton, and the glass transition temperature of the homopolymer is -70°C or more and 180°C The following monomers are used as monomer units. For example, the polarizing film with adhesive layer of claim 1 or 2, which contains a homopolymer with a glass transition temperature of -80°C or more and 0°C or less (meth)acrylic acid alkyl ester (A) 80% by weight or more as the above The monomer unit of the base polymer. For example, the polarizing film with an adhesive layer of claim 3, which further contains at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) 0～ 20% by weight is used as the monomer unit of the above-mentioned base polymer. The polarizing film with an adhesive layer according to any one of claims 1 to 4, wherein the weight average molecular weight Mw of the base polymer is 500,000 to 2.5 million. The adhesive layer-attached polarizing film of any one of claims 1 to 5, wherein the melting temperature of the polysiloxane oligomer Ps is -20 to 120°C.

Images